CN116376429A - Black polyimide coating and preparation method thereof - Google Patents
Black polyimide coating and preparation method thereof Download PDFInfo
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- CN116376429A CN116376429A CN202310440608.5A CN202310440608A CN116376429A CN 116376429 A CN116376429 A CN 116376429A CN 202310440608 A CN202310440608 A CN 202310440608A CN 116376429 A CN116376429 A CN 116376429A
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- carbon black
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- 238000000576 coating method Methods 0.000 title claims abstract description 71
- 239000011248 coating agent Substances 0.000 title claims abstract description 68
- 229920001721 polyimide Polymers 0.000 title claims abstract description 57
- 239000004642 Polyimide Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000006229 carbon black Substances 0.000 claims abstract description 73
- 239000000178 monomer Substances 0.000 claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 claims abstract description 49
- 239000002184 metal Substances 0.000 claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 36
- 150000004985 diamines Chemical class 0.000 claims abstract description 34
- 239000002002 slurry Substances 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000004952 Polyamide Substances 0.000 claims abstract description 20
- 229920002647 polyamide Polymers 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- 239000002798 polar solvent Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000003973 paint Substances 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims description 17
- -1 aromatic isocyanate Chemical class 0.000 claims description 16
- 239000012948 isocyanate Substances 0.000 claims description 16
- 238000010008 shearing Methods 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000004984 aromatic diamines Chemical group 0.000 claims description 6
- 229920005575 poly(amic acid) Polymers 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 238000012360 testing method Methods 0.000 description 11
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a black polyimide coating and a preparation method thereof, wherein the method comprises the following steps: s1, dispersing carbon black and a dispersing agent in a first polar solvent of a non-proton type to obtain carbon black slurry; dispersing a curing agent in a non-ionic second polar solvent to obtain a curing agent solution; s2, sequentially adding diamine monomer and dianhydride monomer into the carbon black slurry, then adding a curing agent solution, and stirring for a period of time to obtain polyamide acid paint; and S3, coating the metal substrate with the polyamide acid coating after defoaming, heating in stages, and performing thermal imidization to obtain the metal-based polyimide coating. The invention improves the adhesive force between the polyimide coating and the surface of the metal plate by adding the curing agent, reduces the addition amount of carbon black and improves the insulating property of the film.
Description
Technical Field
The invention particularly relates to a black polyimide coating and a preparation method thereof.
Background
Polyimide is a polymer with imide ring as characteristic structure, has the characteristics of high heat resistance, high chemical stability, excellent mechanical and dielectric properties, good impact resistance, radiation resistance, solvent resistance and the like, and is widely applied to the industries of aerospace, electronic electrician, automobiles and the like.
Patent CN115678421a proposes a high heat conduction aluminum-based liquid-cooled substrate and a preparation method thereof, the high heat conduction aluminum-based liquid-cooled substrate comprises an aluminum plate and a polyimide layer coated on the aluminum plate; the polyimide layer comprises polyimide and graphene/Cu uniformly dispersed in the polyimide 2 O complex, graphene/Cu 2 The O compound is used as a high heat conduction filler, and can effectively improve the heat dissipation efficiency of the obtained liquid cooling plate base material. The surface of the aluminum plate is provided with a large number of hydroxyl groups, the hydroxyl groups in polyimide with hydroxyl groups in a molecular chain can be in hydrogen bond combination with the hydroxyl groups of the aluminum plate, and the peel strength of a polyimide layer coated on the aluminum plate can be enhanced, but the intermolecular strength is general, the hydrogen bond is easy to break at high temperature, and the peel strength between coatings is weakened.
Patent CN115521706a provides a preparation method of polyimide glue solution, which comprises the following steps: providing color paste, wherein the color paste is a dispersion of carbon black in an aprotic polar solvent, mixing the color paste, a wetting dispersant and polyimide resin, dispersing to obtain polyimide glue solution, and drying the polyimide glue solution to obtain a black film, wherein the black film has low light transmittance, uniform blackness and good insulation. The black film prepared by adding the carbon black has low light transmittance and protects the copper sheet from photo-oxidation, but the carbon black has good conductivity, so that the insulating property of the polyimide black film is reduced, and the possibility of insulation failure is increased.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a black polyimide coating and a preparation method thereof, and the invention improves the adhesion between the polyimide coating and the surface of a metal plate by adding a curing agent, reduces the addition amount of carbon black and improves the insulating property of a film.
The technical scheme of the invention is as follows:
a preparation method of a black polyimide coating comprises the following steps:
s1, preparing carbon black slurry and curing agent solution
Dispersing carbon black and a dispersing agent in a first polar solvent of a non-proton type to obtain carbon black slurry; dispersing a curing agent in a non-ionic second polar solvent to obtain a curing agent solution;
s2, preparation of polyamic acid paint
Adding diamine monomer and dianhydride monomer into the carbon black slurry in sequence, then adding a curing agent solution, and stirring for a period of time to obtain polyamide acid paint; the solid polymer synthesized from diamine and dianhydride is called polyamic acid (PAA);
s3, preparing a metal-based polyimide coating
And (3) after defoaming the polyamic acid coating, coating the coating on a metal substrate, heating the metal substrate in stages, and performing thermal imidization to obtain the metal-based polyimide coating.
Preferably, in the step S1, the ratio of the mass of the carbon black to the sum of the mass of the diamine monomer and the mass of the dianhydride monomer is (0.010 to 0.030): 1, wherein the ratio of the mass of the curing agent to the sum of the mass of the diamine monomer and the mass of the dianhydride monomer is (0.005-0.15): 1. further preferably, the ratio of the mass of the carbon black to the sum of the mass of the diamine monomer and the mass of the dianhydride monomer is (0.020 to 0.030): 1, wherein the ratio of the mass of the curing agent to the sum of the mass of the diamine monomer and the mass of the dianhydride monomer is (0.02-0.15): 1. still more preferably, the ratio of the mass of the carbon black to the sum of the mass of the diamine monomer and the mass of the dianhydride monomer is (0.020 to 0.025): 1, wherein the ratio of the mass of the curing agent to the sum of the mass of the diamine monomer and the mass of the dianhydride monomer is (0.05-0.07): 1.
preferably, the ratio of the mass of the dispersant to the mass of the carbon black is (0.01 to 0.5): 1.
further preferably, the ratio of the mass of the carbon black to the sum of the mass of the diamine monomer and the mass of the dianhydride monomer is (0.010 to 0.030): 1
Preferably, in the step S1, the curing agent is an aromatic isocyanate and/or an aliphatic isocyanate.
Preferably, in the step S1, the dispersion mode in the preparation of the carbon black slurry is ultrasonic shearing dispersion, the frequency is 5 kHz-20 kHz, the shearing speed is 2000-4000 rpm, and the dispersion time is 30-200 min.
Preferably, the first polar solvent is any one or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide; the second polar solvent is one or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
Preferably, the ratio of the sum of the mass of the diamine monomer and the dianhydride monomer to the sum of the mass of the first polar solvent and the mass of the second polar solvent is (0.1 to 0.3): 1.
preferably, in the step S2, the diamine monomer is an aromatic diamine, the dianhydride monomer is an aromatic tetracarboxylic dianhydride, and the molar ratio of the aromatic diamine to the aromatic tetracarboxylic dianhydride is 1:0.99 to 1:1.02.
preferably, the aromatic diamine comprises at least p-phenylenediamine, wherein the amount of p-phenylenediamine is 10% -40% of the total diamine component materials.
Preferably, in step S3, the stage temperature is raised as follows: heating the metal plate to 80-120 ℃, preserving heat for 40-100 min, heating to 160-180 ℃, preserving heat for 20-40 min, heating to 300-350 ℃, preserving heat for 20-40 min, heating to 450 ℃ and preserving heat for 20-60 min.
The invention also relates to a black polyimide coating, which is prepared by adopting the preparation method.
The beneficial effects of the invention are as follows:
(1) According to the invention, the curing agent is added to chemically crosslink with hydroxyl groups on the surface of the metal plate to form a covalent bond, and meanwhile, the epoxy resin can react with moisture generated on the surface of the metal plate or in amination of Wen Ya, so that urea bonds are produced and then hydrogen bonds are produced with metal oxides, and the adhesive force between the polyimide coating and the surface of the metal plate is improved;
(2) According to the invention, the curing agent is added to generate polymerization reaction or reaction with amino in polyamide acid at high temperature to produce new compounds, and the black substances are dark and black, so that the light transmittance of the polyimide film can be reduced, the addition amount of carbon black is reduced, and the insulating property of the film is improved;
(3) The polyimide coating prepared by the invention has the characteristics of high cohesiveness, high shading degree and high electrical insulation.
Detailed Description
The present invention will be further described in detail with reference to the following embodiments, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
The test methods and calculation methods of the respective indexes involved in the following examples and comparative examples are as follows:
1) Adhesion test: and (3) drawing 6 parallel cuts with equal spacing (the thickness of the coating in the experiment is about 12.5 mu m, and the spacing is 1 mm) on the metal-based polyimide coating by using a special hundred grid knife for coating, and then vertically cutting the cuts with the same number and spacing as those of the former cuts to form a 5X 5 square with 25 grids. When the hundred knives are cut down, the substrates should be cut, and the substrates cannot be cut on the paint, otherwise, the test is not established. The adhesive tape is adhered to the position of the hundred grids, the adhesive tape is tightly adhered by pressing with fingers, then the adhesive tape is torn up, and whether the coating on the substrate is fallen off or not is visually checked.
2) Test of breakdown strength: the metal-based polyimide coating is immersed in a weak acid and then the polyimide coating is peeled off. And an electrical breakdown strength tester is adopted to test the electrical breakdown strength of the polyimide coating, and the test standard GB/T1408.1-2016 (test method for electrical strength of insulating materials).
3) Transmittance test (transmittance test performed in the visible light range): adopting a UV-visible spectrophotometer to scan and test the 280-800nm wave band interval, and testing the standard: GT/T2410-2008 determination of light transmittance and haze of transparent plastics.
Comparative example 1
In this comparative example, no curing agent was added, and the amount of carbon black added was 2% of the sum of the mass of the diamine monomer and the mass of the dianhydride monomer, and the amount of BYK9076 (dispersant) added was 15% of the mass of the carbon black.
(1) Preparing carbon black slurry: 1.2g of carbon black and 0.18g of BYK9076 were added to 240g of DMAc (N, N-dimethylacetamide) solution to conduct ultrasonic shearing dispersion at a frequency of 10kHz at a shearing speed of 3000rpm, and after dispersion for 120 minutes, a carbon black slurry was obtained.
(2) Preparation of polyamide acid paint: transferring the carbon black slurry obtained in the step (1) to a reaction kettle, adding 4.98g of p-phenylenediamine, then adding 8.04g of pyromellitic dianhydride, then adding 21.52g of 4,4' -diaminodiphenyl ether, finally adding 25.46g of pyromellitic dianhydride, and stirring for 2 hours to obtain the polyamide acid coating with the solid content of 20%.
(3) Preparing a metal-based polyimide coating: and (3) coating the polyamide acid coating obtained in the step (2) on a metal plate after defoaming, heating the metal plate to 120 ℃ in a stage heating mode, preserving heat for 40min, heating to 180 ℃ in a heat preserving mode, heating to 350 ℃ in a heat preserving mode for 20min, heating to 450 ℃ in a heat preserving mode for 40min, and obtaining the metal-based polyimide coating with the thickness of 12.5 mu m.
Comparative example 2
Comparative example 2 a metal-based polyimide coating was prepared in the same manner as in comparative example 1 except that the amount of carbon black added was changed as compared with comparative example 1, the amount of carbon black added in comparative example 2 was 2.5% of the sum of the mass of diamine monomer and dianhydride monomer, and the amount of BYK9076 (dispersant) added was still 15% of the mass of carbon black.
Comparative example 3
Comparative example 3 a metal-based polyimide coating was prepared in the same manner as in comparative example 1 except that the amount of carbon black added was changed as compared with comparative example 1, the amount of carbon black added in comparative example 2 was 3% of the sum of the mass of diamine monomer and dianhydride monomer, and the amount of BYK9076 (dispersant) added was still 15% of the mass of carbon black.
Example 1
In the embodiment, aliphatic isocyanate is selected as a curing agent, and the addition amount is 5% of the sum of the mass of diamine monomer and dianhydride monomer; the addition amount of the carbon black is 2% of the sum of the mass of the diamine monomer and the mass of the dianhydride monomer, and the addition amount of BYK9076 (dispersing agent) is 15% of the mass of the carbon black.
(1) Preparing carbon black slurry and curing agent solution: 1.2g of carbon black and 0.18g of BYK9076 were added to 220g of DMAc solution for ultrasonic shearing dispersion at a frequency of 10kHz at a shearing speed of 3000rpm, and after dispersion for 120 minutes, a carbon black slurry was obtained.
3g of aliphatic isocyanate (hexamethylene diisocyanate) was added to 20g of DMAC solution and stirred at 300rpm for 10 minutes to obtain a curing agent solution.
(2) Preparation of polyamide acid paint: transferring the carbon black slurry obtained in the step (1) to a reaction kettle, adding 4.98g of p-phenylenediamine, adding 8.04g of pyromellitic dianhydride, adding 21.52g of 4,4' -diaminodiphenyl ether, adding 25.46g of pyromellitic dianhydride, stirring for 2 hours, and finally adding the curing agent solution obtained in the step (1), and stirring for 20 minutes to obtain the polyamide acid coating with the solid content of 20%.
(3) Preparing a metal-based polyimide coating: and (3) coating the polyamide acid coating obtained in the step (2) on a metal plate after defoaming, heating the metal plate to 120 ℃ in a stage heating mode, preserving heat for 40min, heating to 180 ℃ in a heat preserving mode, heating to 350 ℃ in a heat preserving mode for 20min, heating to 450 ℃ in a heat preserving mode for 40min, and obtaining the metal-based polyimide coating with the thickness of 12.5 mu m.
Example 2
Example 2 in comparison with example 1, a metal-based polyimide coating was prepared in the same manner as in example 1 except that the amount of carbon black added was changed, the amount of carbon black added in example 2 was 2.5% of the sum of the mass of the diamine monomer and the mass of the dianhydride monomer, and the amount of BYK9076 (dispersant) added was still 15% of the mass of the carbon black.
Example 3
In the embodiment, aliphatic isocyanate is selected as a curing agent, and the addition amount is 7% of the sum of the mass of diamine monomer and dianhydride monomer; the addition amount of the carbon black is 2% of the sum of the mass of the diamine monomer and the mass of the dianhydride monomer, and the addition amount of BYK9076 (dispersing agent) is 15% of the mass of the carbon black.
(1) Preparing carbon black slurry and curing agent solution: 1.2g of carbon black and 0.18g of BYK9076 were added to 210g of DMAc solution for ultrasonic shearing dispersion at a frequency of 10kHz at a shearing speed of 3000rpm, and after dispersion for 120 minutes, a carbon black slurry was obtained.
4.2g of aliphatic isocyanate (hexamethylene diisocyanate) was added to 30g of DMAC solution and stirred at 300rpm for 10 minutes to obtain a curing agent solution.
(2) Preparation of polyamide acid paint: transferring the carbon black slurry obtained in the step (1) to a reaction kettle, adding 4.98g of p-phenylenediamine, adding 8.04g of pyromellitic dianhydride, adding 21.52g of 4,4' -diaminodiphenyl ether, adding 25.46g of pyromellitic dianhydride, stirring for 2 hours, and finally adding the curing agent solution obtained in the step (1), stirring for 25 minutes to obtain the polyamide acid coating with the solid content of 20%.
(3) Preparing a metal-based polyimide coating: and (3) coating the polyamide acid coating obtained in the step (2) on a metal plate after defoaming, heating the metal plate to 120 ℃ in a stage heating mode, preserving heat for 40min, heating to 180 ℃ in a heat preserving mode, heating to 350 ℃ in a heat preserving mode for 20min, heating to 450 ℃ in a heat preserving mode for 40min, and obtaining the metal-based polyimide coating with the thickness of 12.5 mu m.
Example 4
Example 4 in comparison with example 3, a metal-based polyimide coating was prepared in the same manner as in example 3, except that the amount of carbon black added was changed, the amount of carbon black added in example 4 was 2.5% of the sum of the mass of diamine monomer and dianhydride monomer, and the amount of BYK9076 (dispersant) added was still 15% of the mass of carbon black.
Example 5
Example 5 in comparison with example 1, a metal-based polyimide coating was prepared in the same manner as in example 1, except that the type of curing agent was changed, and an aromatic isocyanate curing agent (4, 4' -diphenylmethane diisocyanate) was selected in example 5.
Example 6
Example 6a metal-based polyimide coating was prepared in the same manner as in example 3, except that the kind of the curing agent was changed as compared with example 3, and an aromatic isocyanate curing agent (4, 4' -diphenylmethane diisocyanate) was selected in example 6.
Example 7
In the embodiment, aliphatic isocyanate is selected as a curing agent, and the addition amount is 0.5% of the sum of the mass of diamine monomer and dianhydride monomer; the addition amount of the carbon black is 2% of the sum of the mass of the diamine monomer and the mass of the dianhydride monomer, and the addition amount of BYK9076 (dispersing agent) is 15% of the mass of the carbon black.
(1) Preparing carbon black slurry and curing agent solution: 1.2g of carbon black and 0.18g of BYK9076 were added to 230g of DMAc solution for ultrasonic shearing dispersion at a frequency of 10kHz at a shearing speed of 3000rpm, and after dispersion for 120 minutes, a carbon black slurry was obtained.
0.3g of aliphatic isocyanate (hexamethylene diisocyanate) was added to 10g of DMAC solution and stirred at 300rpm for 10 minutes to obtain a curing agent solution.
(2) Preparation of polyamide acid paint: transferring the carbon black slurry obtained in the step (1) to a reaction kettle, adding 4.98g of p-phenylenediamine, adding 8.04g of pyromellitic dianhydride, adding 21.52g of 4,4' -diaminodiphenyl ether, adding 25.46g of pyromellitic dianhydride, stirring for 2 hours, and finally adding the curing agent solution obtained in the step (1), and stirring for 10 minutes to obtain the polyamide acid coating with the solid content of 20%.
(3) Preparing a metal-based polyimide coating: and (3) coating the polyamide acid coating obtained in the step (2) on a metal plate after defoaming, heating the metal plate to 120 ℃ in a stage heating mode, preserving heat for 40min, heating to 180 ℃ in a heat preserving mode, heating to 350 ℃ in a heat preserving mode for 20min, heating to 450 ℃ in a heat preserving mode for 40min, and obtaining the metal-based polyimide coating with the thickness of 12.5 mu m.
Example 8
In the embodiment, aliphatic isocyanate is selected as a curing agent, and the addition amount is 2% of the sum of the mass of diamine monomer and dianhydride monomer; the addition amount of the carbon black is 2% of the sum of the mass of the diamine monomer and the mass of the dianhydride monomer, and the addition amount of BYK9076 (dispersing agent) is 15% of the mass of the carbon black.
(1) Preparing carbon black slurry and curing agent solution: 1.2g of carbon black and 0.18g of BYK9076 were added to 225g of DMAc solution for ultrasonic shearing dispersion at a frequency of 10kHz at a shearing speed of 3000rpm, and after dispersion for 120 minutes, a carbon black slurry was obtained.
1.2g of aliphatic isocyanate (hexamethylene diisocyanate) was added to 15g of a DMAC solution and stirred at 300rpm for 10 minutes to obtain a curing agent solution.
(2) Preparation of polyamide acid paint: transferring the carbon black slurry obtained in the step (1) to a reaction kettle, adding 4.98g of p-phenylenediamine, adding 8.04g of pyromellitic dianhydride, adding 21.52g of 4,4' -diaminodiphenyl ether, adding 25.46g of pyromellitic dianhydride, stirring for 2 hours, and finally adding the curing agent solution obtained in the step (1), stirring for 15 minutes to obtain the polyamide acid coating with the solid content of 20%.
(3) Preparing a metal-based polyimide coating: and (3) coating the polyamide acid coating obtained in the step (2) on a metal plate after defoaming, heating the metal plate to 120 ℃ in a stage heating mode, preserving heat for 40min, heating to 180 ℃ in a heat preserving mode, heating to 350 ℃ in a heat preserving mode for 20min, heating to 450 ℃ in a heat preserving mode for 40min, and obtaining the metal-based polyimide coating with the thickness of 12.5 mu m.
Example 9
Example 9 in comparison with example 1, a metal-based polyimide coating was prepared in the same manner as in example 1, except that the amount of carbon black added was changed, and in example 9, the amount of carbon black added was 3% of the sum of the mass of the diamine monomer and the mass of the dianhydride monomer, and the amount of BYK9076 (dispersant) added was still 15% of the mass of the carbon black.
Example 10
Example 10 in comparison with example 3, a metal-based polyimide coating was prepared in the same manner as in example 3, except that the amount of carbon black added was changed, the amount of carbon black added in example 10 was 3% of the sum of the mass of the diamine monomer and the dianhydride monomer, and the amount of BYK9076 (dispersant) added was still 15% of the mass of the carbon black.
Example 11
Example 11 in comparison with example 7, a metal-based polyimide coating was prepared in the same manner as in example 7, except that the kind of the curing agent was changed, and an aromatic isocyanate curing agent (4, 4' -diphenylmethane diisocyanate) was selected in example 11.
Example 12
Example 12 in comparison with example 8, a metal-based polyimide coating was prepared in the same manner as in example 8, except that the kind of the curing agent was changed, and an aromatic isocyanate curing agent (4, 4' -diphenylmethane diisocyanate) was selected in example 12.
The main parameter conditions and test results of the above comparative examples 1 to 3 and examples 1 to 12 were compared as shown in Table 1.
TABLE 1 Main parameter conditions and test results for comparative examples 1-3 and examples 1-12
As can be seen from examples in Table 1, the present invention improves the properties of polyimide coatings, particularly examples 1 to 6, by adding a curing agent, compared with comparative examples 1 to 3, and it can be seen from examples 1 to 6 that polyimide coatings having an ASTM grade of 5B, a light transmittance of 0.3% or less, and a breakdown strength of 150kv/mm, and having high adhesion, high light shielding, and high electrical insulation can be produced by the production method of the present invention.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and are in no way limiting of the invention. Accordingly, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present invention should be included in the scope of the present invention. Furthermore, the appended claims are intended to cover all such changes and modifications that fall within the scope and boundary of the appended claims, or equivalents of such scope and boundary.
Claims (10)
1. The preparation method of the black polyimide coating is characterized by comprising the following steps of:
s1, preparing carbon black slurry and curing agent solution
Dispersing carbon black and a dispersing agent in a first polar solvent of a non-proton type to obtain carbon black slurry; dispersing a curing agent in a non-ionic second polar solvent to obtain a curing agent solution;
s2, preparation of polyamic acid paint
Adding diamine monomer and dianhydride monomer into the carbon black slurry in sequence, then adding a curing agent solution, and stirring for a period of time to obtain polyamide acid paint;
s3, preparing a metal-based polyimide coating
And (3) after defoaming the polyamic acid coating, coating the coating on a metal substrate, heating the metal substrate in stages, and performing thermal imidization to obtain the metal-based polyimide coating.
2. The production method according to claim 1, wherein in the step S1, the ratio of the mass of the carbon black to the sum of the mass of the diamine monomer and the mass of the dianhydride monomer is (0.010 to 0.030): 1, wherein the ratio of the mass of the curing agent to the sum of the mass of the diamine monomer and the mass of the dianhydride monomer is (0.005-0.15): 1.
3. the method according to claim 1, wherein in the step S1, the ratio of the mass of the dispersant to the mass of the carbon black is (0.01 to 0.5): 1.
4. the method according to claim 1, wherein in step S1, the curing agent is an aromatic isocyanate and/or an aliphatic isocyanate.
5. The method according to claim 1, wherein in the step S1, the dispersion mode is ultrasonic shearing dispersion, the frequency is 5 kHz-20 kHz, the shearing speed is 2000 rpm-4000 rpm, and the dispersion time is 30-200 min.
6. The preparation method according to claim 1, wherein the first polar solvent is any one or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide; the second polar solvent is one or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide; the ratio of the sum of the masses of the diamine monomer and the dianhydride monomer to the sum of the masses of the first polar solvent and the second polar solvent is (0.1 to 0.3): 1.
7. the method according to claim 1, wherein in step S2, the diamine monomer is an aromatic diamine, the dianhydride monomer is an aromatic tetracarboxylic dianhydride, and the molar ratio of the aromatic diamine to the aromatic tetracarboxylic dianhydride is 1:0.99 to 1:1.02.
8. the method of claim 7, wherein the aromatic diamine comprises at least p-phenylenediamine, and wherein the amount of p-phenylenediamine is from 10% to 40% of the total diamine component material.
9. The method according to claim 1, wherein in step S3, the stage temperature rise is: heating the metal plate to 80-120 ℃, preserving heat for 40-100 min, heating to 160-180 ℃, preserving heat for 20-40 min, heating to 300-350 ℃, preserving heat for 20-40 min, heating to 450 ℃ and preserving heat for 20-60 min.
10. A black polyimide coating prepared by the preparation method of any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107216471A (en) * | 2017-08-02 | 2017-09-29 | 桂林电器科学研究院有限公司 | A kind of preparation method of multilayer black matt polyimide film |
| WO2019093669A2 (en) * | 2017-11-10 | 2019-05-16 | 에스케이씨코오롱피아이 주식회사 | Ultra-thin black polyimide film and manufacturing method therefor |
| CN112679953A (en) * | 2020-12-28 | 2021-04-20 | 安徽省长荣新材料科技有限公司 | High-insulation-strength black matte polyimide film and preparation process thereof |
| CN114752081A (en) * | 2022-03-23 | 2022-07-15 | 山东万达微电子材料有限公司 | Preparation method of carbon black dispersion liquid for black polyimide film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107216471A (en) * | 2017-08-02 | 2017-09-29 | 桂林电器科学研究院有限公司 | A kind of preparation method of multilayer black matt polyimide film |
| WO2019093669A2 (en) * | 2017-11-10 | 2019-05-16 | 에스케이씨코오롱피아이 주식회사 | Ultra-thin black polyimide film and manufacturing method therefor |
| CN112679953A (en) * | 2020-12-28 | 2021-04-20 | 安徽省长荣新材料科技有限公司 | High-insulation-strength black matte polyimide film and preparation process thereof |
| CN114752081A (en) * | 2022-03-23 | 2022-07-15 | 山东万达微电子材料有限公司 | Preparation method of carbon black dispersion liquid for black polyimide film |
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Effective date of registration: 20240815 Address after: No. 8 Cifu Road, Economic and Technological Development Zone, Shuyang County, Suqian City, Jiangsu Province, 223600 Patentee after: Jiangsu Keze Optoelectronic Materials Co.,Ltd. Country or region after: China Address before: 2nd Floor, Zone C, Building C, No. 30 Jingdong Road, Weiting Street, Industrial Park, Suzhou City, Jiangsu Province, 215121 Patentee before: Suzhou Corell Chemical Co.,Ltd. Country or region before: China |